Viscoelastic phase diagram of fluorinated and grafted polymer films and proton-exchange membranes for fuel cell applications

The influence of temperature and moisture activity on the viscoelastic behavior of fluorinated membranes for fuel cell applications was investigated. Uncrosslinked and crosslinked ethylene tetrafluoroethylene (ETFE)-based proton-conducting membranes were prepared by radiation grafting and subsequent sulfonation and their behavior was compared with ETFE base film and commercial Nafion (R) NR212 membrane. Uniaxial tensile tests and stress relaxation tests at controlled temperature and relative humidity (RH) were carried out at 30 and 50 degrees C for 10%60%, with an almost single relaxation time exponential. An exponential decrease of relaxation time with RH from 60 s to 10 s was obtained at RH70% and 30 degrees C. The general behavior of grafted films observed at 30 degrees C was also obtained at 50 degrees C. However, an anomalous result was noticed for the membranes, with a higher modulus at 50 degrees C when compared with 30 degrees C. This behavior was explained by solvation of the sulfonic acid groups by water absorption creating hydrogen bonding within the clusters. A viscoelastic phase diagram was elaborated to map critical conditions (temperature and RH) for transitions in time-dependent behavior, from power-law scaling to exponential scaling. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1139-1148